CN101965340A - Membrane separation method for separating high boiler during the production of 1,3-dioxolane-2-ones - Google Patents
Membrane separation method for separating high boiler during the production of 1,3-dioxolane-2-ones Download PDFInfo
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- CN101965340A CN101965340A CN2009801070831A CN200980107083A CN101965340A CN 101965340 A CN101965340 A CN 101965340A CN 2009801070831 A CN2009801070831 A CN 2009801070831A CN 200980107083 A CN200980107083 A CN 200980107083A CN 101965340 A CN101965340 A CN 101965340A
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- 239000012528 membrane Substances 0.000 title claims abstract description 42
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- 238000000926 separation method Methods 0.000 title claims description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 82
- 238000000034 method Methods 0.000 claims abstract description 60
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 238000007599 discharging Methods 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 29
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 28
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- 239000007788 liquid Substances 0.000 claims description 20
- 230000014759 maintenance of location Effects 0.000 claims description 18
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- 239000007791 liquid phase Substances 0.000 claims description 13
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- 230000009471 action Effects 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
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- 230000002427 irreversible effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- 229910052723 transition metal Inorganic materials 0.000 description 2
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
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- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
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- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- 230000035699 permeability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VFJYIHQDILEQNR-UHFFFAOYSA-M trimethylsulfanium;iodide Chemical compound [I-].C[S+](C)C VFJYIHQDILEQNR-UHFFFAOYSA-M 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
- C07D317/38—Ethylene carbonate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Compounds (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Polyethers (AREA)
Abstract
The invention relates to a method for the continuous production of a 1,3-dioxolane-2-one of formula (I) where R1 represents hydrogen or an organic radical comprising 1 to 40 carbon atoms and R2 and R3, which can also be bonded to one another to form a five-membered or six-membered ring, independently represent hydrogen or C1-C4 alkyl. In said method, a product from the reaction zone is separated by means of a semipermeable membrane in order to separate secondary polymer products.
Description
The present invention relates to a kind of continuous preparation 1, the method for 3-dioxolane-2-ketone, wherein the reaction zone discharging is carried out classification to isolate polymeric by-products by semi-permeable membranes.
Prepare 1 by respective rings oxide compound (for example ethylene oxide or propylene oxide) is reacted in the presence of the catalyzer that evenly is dissolved in the liquid phase in liquid phase with carbonic acid gas, 3-dioxolane-2-ketone such as ethylene carbonate or Texacar PC are known.This method for example is described among DE 19819586 A1.The aftertreatment of reaction discharging, promptly removing to be recycled in the reaction zone of the separation of product and catalyzer undertaken by currently known methods such as distillation, extraction or stripping.Conventional procedure comprises that the bottoms that goes out low-boiling-point substance and product and will comprise catalyzer subsequently by fractionation by distillation is recycled in the reaction.The shortcoming of this program is the height by product that boils of reaction, and for example ring-type and the linear polyether that is produced by used epoxide accumulates in the reaction system.These molecular weight can cause the increase of catalyst recycle materials flow viscosity up to about 20000 daltonian high boiling material.For example, therefore have to the distillation substrate that is rich in high boiling material is regularly removed from system with the catalyzer that wherein exists by in the distillatory aftertreatment.This causes this method and produces detrimentally affect economically because of catalyzer that required shut-down of equipment and high boiling material processing produce and product loss.Therefore need a kind of continuous preparation 1 that does not have these shortcomings, the method for 3-dioxolane-2-ketone.
Semi-permeable membranes is isolated the homogeneous catalyzer in synthesizing continuously purposes is known.These methods for example are described among DE 10328713 A1 and DE 10328715 A1.Yet these methods are intended to solve chemically different problems, i.e. two kinds of additions that have the terminal olefin of at least two functional groups.From preparation 1, in the reaction discharging of 3-dioxolane-2-ketone, also as 1 of reaction solvent, 3-dioxolane-2-ketone and catalyzer obtain with mixture high boiling material with usually in aftertreatment.Because 1,3-dioxolane-2-ketone form the balanced reaction that is different from chemical action described in DE 10328713 A1 and DE 10328715 A1, should anticipate in this case by the epoxide that forms in the reversed reaction (for example by epoxide and reactive functional groups on the film surface and/or the reaction in the fenestra) or deposit the irreversible obstruction of film that causes on film or in the film by the polymerisate of epoxide.In addition, should anticipate that the further addition by epoxide makes the chain extension that is deposited on the polymkeric substance in film surface or the fenestra will play negative influence for the irreversible obstruction of film.
Now be surprisingly found out that, can height be boiled (polymerization) by product from 1, isolate in the reaction discharging of 3-dioxolane-2-ketone by membrane separating method.The special high boiling material that surprisingly separates from the membrane sepn retention can or be accumulated in the remarkable decline that occurs membrane permeability on the film surface and/or in the fenestra not owing to polymer deposition.Therefore method of the present invention also is favourable for the polymeric by-products of removing formation continuously.The regular shut-down of equipment and the uneconomical loss of catalyzer can be avoided.
Therefore, the invention provides 1 of a kind of continuous preparation general formula I, the method for 3-dioxolane-2-ketone,
Wherein
R
1For hydrogen or have the organic group of 1-40 carbon atom,
R
2And R
3Be hydrogen or C separately independently of each other
1-C
4Alkyl, wherein R
2And R
3Also can mutually combine forms five yuan or six-ring,
Wherein:
A) epoxide of general formula I I and carbonic acid gas are reacted in liquid phase in the presence of the catalyzer that evenly is dissolved in the liquid phase,
R wherein
1, R
2And R
3As defined above,
B) from reaction zone, take out and comprise the liquid discharging of reactive polymeric by product and comprise by the aftertreatment of semi-permeable membranes fractionated to obtain penetrant and retention, wherein the high molecular weight block tunicle of polymeric by-products keep and
C) provide the purge flow that comprises the polymeric by-products high molecular weight block by retention.
The preparation of compound (I) causes forming the height by product that boils, and it is mainly oligopolymer and the polymkeric substance that is derived from the epoxide (II) that is used to react.These oligopolymer and polymkeric substance can be linearity and ring compound.These by products are summarized by term " polymeric by-products " for the purpose of the present invention.
Because the continuous mode that reaction is carried out, the molecular weight that is included in the polymeric by-products in the reaction zone discharging increases up to the separation extreme that reaches used film when the inventive method begins at first.After this, produce basicly stable state owing to remove high molecular weight block from system, i.e. the concentration of polymeric by-products no longer significantly increases in the reaction zone discharging.For the purpose of the present invention, " high molecular weight block " of polymeric by-products is the component that keeps by film." low molecular weight fraction " of polymeric by-products is correspondingly for entering fraction in the penetrant (promptly for the purpose of the present invention, the separation extreme of used film has determined what is that to divide with what be the high molecular weight block of polymeric by-products for the low sub-magnitude of polymeric by-products) by semi-permeable membranes.Other higher molecular weight by product is by being recycled to low molecular weight fraction in the reaction with catalyzer as the further addition result of epoxide and form.
Use to comprise usually to small part by the classification of semi-permeable membranes in the step b) to be included in 1 of catalyzer in the liquid discharging of reaction zone and general formula I, 3-dioxolane-2-ketone (product) carries out as the materials flow of other component.Advantageously catalyzer and product to small part enters in the penetrant.Also comprise in the preferable methods: d) penetrant is recycled at least in part in the aftertreatment of reaction zone in the step a) and/or step b).
Carry out in the reaction zone of that epoxide (II) and carbonic acid gas being reflected in step a) can have is one or more (for example two, three or more than three) reactor.Reactor can be identical or different reactor.These reactors can for example have identical or different mixed characteristic separately and/or be separated one or many by internals.Be suitable for 1 of preparation formula I, the level pressure reactor of 3-dioxolane-2-ketone is that those skilled in the art are known.They generally include the popular response device that is used for gas-liquid reaction, for example tubular reactor, shell and tube-type reactor, gas circulation reactor, bubble-plate column, loop apparatus, stirred vessel (it also can be configured to the stirred vessel cascade), airlift reactor etc.
The method that is suitable for reacting in two portions reactor is described among the DE 19819586, wherein in first part, be reflected under the backmixing and proceed to conversion rate of epoxide at least 80%, in second section, be reflected under the non-backmixing condition and carry out, wherein carbonic acid gas is delivered in the epoxide with adverse current by the entire reaction district, this method is incorporated herein by reference fully at this.
Temperature is generally about 60-160 ℃ in the reaction of step a), and preferred 70-150 ℃, preferred 90-145 ℃ especially.Be reflected at when carrying out in the reactor, the temperature in each post-reactor can be arranged to preceding reactor in the different value of temperature.In specific embodiments, each post-reactor is operated under than the higher temperature of preceding reactor.In addition, each reactor can have two or more reaction zones of operating under differing temps.Therefore, for example different with first reaction zone, preferably higher than first reaction zone temperature can be set in second reaction zone, or the temperature higher than preceding reaction zone is set in each afterreaction district, for example transform to reach very completely.
Reaction pressure is generally about 2-50 crust in step a), preferred especially 5-40 crust, especially 10-30 crust.Need, under the situation of using a plurality of reactors, the pressure of different with preceding reactor (preferably higher) can be set in each post-reactor.
Can with feed carbon dioxide and epoxide with and stream or adverse current carry and pass through reaction zone.Also carbonic acid gas and epoxide can be carried by another part reaction zone also to flow to carry by a part of reaction zone and with adverse current in embodiments.Preferably carbonic acid gas and epoxide are carried by the entire reaction district with adverse current.
According to the present invention, liquid discharging is taken out from reaction zone and is used for subsequently aftertreatment.In addition, the gaseous state discharging can be in reactor head, or comprises at reaction zone under the situation of several reactors, and take out at the top of a reactor therein.It comprises unreacted carbonic acid gas and other gaseous state composition of presumable words such as epoxide (II) and/or rare gas element (rare gas, nitrogen).Need, the gaseous state discharging can partly or entirely be recycled in the reaction zone.Need, the gaseous state discharging can partly or entirely be removed from system to avoid inertia gaseous state composition to gather in reaction zone.
Catalyzer as the inventive method, can will be used for this reaction, preferably will by document such as US-A 2773070, US-A2773881, the 517th page of the 1261st page of Chem.Lett. (1979), Chem.Lett. (1979), DE-A3529263, DE-B 1169459, EP-A 069494 or EP-B 543249 known catalyzer
Salt or metal-salt or its mixture are as catalyzer.
Suitable
Salt be in principle all compounds of the type, the especially ammonium salt of general formula III a-IIIc,
Salt and sulfonium salt:
Wherein substituent R is for having the identical or different alkyl of 1-20 carbon atom separately, and in each case in the radicals R the total number of carbon atoms be not more than 24, X
-Be the negatively charged ion Equivalent, preferred halogenide, especially bromide or iodide.
The ammonium salt of preferred formula IIIa, especially tetraethylammonium bromide.In addition, preferably in these compound III a three radicals R be C
1-C
4Alkyl such as methyl or ethyl and the 4th radicals R are benzyl or branching C not
6-C
18Alkyl.
Other preferred catalyzer is for being derived from triphenyl phosphine and its 4th substituting group by using bromination C
1-C
6Quaternary ammonium alkylization and introducing in the molecule
Salt IIIb.
Suitable sulfonium salt IIIc is the trimethyl sulfonium iodide for being easy to prepare for example.Usually, ammonium salt and
Salt is more suitable for than sulfonium salt.
Usually, the alkyl R among the compound III a-IIIc can be branching or preferred nonbranched C
1-C
20Alkyl, aralkyl such as benzyl, cyclohexyl and aromatic group such as phenyl or p-methylphenyl.In addition, alkyl R also can mutually combine, and for example forms piperidine ring.Negatively charged ion can reach for example vitriol and nitrate for halogenide.
Usually, especially in bromination
Situation under, unnecessary from salt IIIa-IIIc itself beginning and use their precursor just enough, i.e. alkali and quaternizing agent, active quaternized products IIIa-IIIc is formed by its original position.
Metal-salt can be the salt of basic metal, alkaline-earth metal and transition metal, especially divalent transition metal, for example the salt of sodium, potassium, magnesium, calcium, aluminium, manganese (II), iron (II), nickel (II), copper (II), zinc, cadmium or lead (II).The negatively charged ion that is applicable to these salt is vitriol, nitrate, phosphoric acid salt, carbonate, acetate, formate and particularly halogenide such as muriate, bromide and iodide.Use zinc salt such as zinc sulfate, zinc nitrate, zinc phosphate, zinc carbonate, zinc acetate, zinc formate, zinc chloride, zinc bromide or zinc iodide to reach good especially result.Can certainly use the mixture of these salt, and equally also be used for above-mentioned
Salt.Can also for
The mixture of salt and metal-salt and under same case, demonstrate surprising advantage.
As catalyzer
The amount of salt and/or metal-salt is inessential usually.Preferable amount is about 0.01-3 weight % based on used epoxide (II).
In preferred embodiments, halogenide or its mixture with alkali metal bromide, alkaline metal iodide, tetraalkyl brometo de amonio, tetraalkyl ammonium iodide, divalent metal is used as catalyzer.
In embodiment very particularly preferably, will
Salt mixture, the especially ammonium salt of general formula III a-IIIc,
Salt and/or sulfonium salt and zinc salt, especially top specifically mentioned those are used as catalyzer.This depend on used epoxide reactive behavior,
Active and other reaction conditions of salt, the significant quantity of zinc salt is based on every mole
Salt is 0.1-1.0mol, preferred 0.3-0.7mol.
The inert solvent that is suitable for the inventive method for example is two
Alkane, toluene or acetone.If solvent is used for reaction, it uses with the amount of about 10-100 weight % based on used epoxide (II) usually.If process products I is a liquid under reaction conditions, then used as solvent, it is favourable being preferably used as unique solvent.Under this class situation, have been found that advantageously catalyzer to be dissolved in this process products and to be metered into this solution, and essentially no other solvent is introduced reactor.At this, catalyst concentration is generally 0.5-20 weight %, especially 1-15 weight % in the process products (I).In the same period the raw material of Jia Ruing (II) is generally 100: 1 to 1: 1, especially 50: 1 to 2: 1 with the mol ratio that is added with the process products (I) of catalyzer.
In the methods of the invention, the incoming flow of epoxide (II) and carbonic acid gas is preferably with 1: 1 to 1: 1.05, and especially 1: 1 to 1: 1.02 mol ratio is used.Excessive carbon dioxide is favourable with the loss of compensation carbonic acid gas when the reaction zone discharging is reduced pressure a little.
Usually the essence Quantitative yield rate of (II) that realizes by the inventive method is generally at least 99%, and especially at least 99.5%, be in particular at least 99.9%.
Suitable R
1Base is:
-hydrogen,
-have 40 carbon atoms at the most, the saturated and undersaturated branching and the non-branching aliphatic group of 18 carbon atoms especially at the most,
-preferably have waiting of 5-7 annular atoms to encircle or the heterocycle alicyclic group,
-wait the ring or the heterocyclic aromatic group and
-have the mixed group of the above-mentioned type group, for example araliphatic group such as a benzyl.
The radicals R that is different from hydrogen
1One or more substituting groups such as halogen, nitro, freedom or the amino, hydroxyl, formyl radical or the cyano group that replace be can have or ether, ketone or ester group comprised.Preferred group R
1Be hydrogen.
Radicals R
2And R
3Be generally hydrogen or methyl or the group of mutually combine five yuan of formation or six-ring, the example is the cyclohexene oxide as Compound I I.If II comprises two and has (CH separately
2) the epoxide ring of group, then obtain corresponding two dioxolane I; The epoxide ring that all replaces on two carbon atoms is usually than those slower react withs that replace on carbon atom only.Preferably ethylene oxide or propylene oxide, particularly ethylene oxide are used as epoxide (II).
In preferred embodiments, ethylene carbonate or Texacar PC prepare by method of the present invention.
According to the present invention, liquid stream takes out and carries out the aftertreatment (step b) of the inventive method as the reaction zone discharging.
The liquid discharging of taking out from reaction zone comprises following component usually:
1 of-general formula I, 3-dioxolane-2-ketone,
-catalyzer,
-polymeric by-products,
-possibility carbon dioxide dissolved,
The epoxide of-possibility dissolved general formula I I.
Aftertreatment in the step b) comprises the membrane separating method as key step.At this, be used for catalyst for reaction and advantageously separate in so much with the high boiling material that forms in reaction: make can from system, remove catalyzer few or the high boiling material materials flow of catalyst-free in the ideal case.
Penetrant preferably comprises (under the multistage membrane sepn situation based on all workshop sections) at least 70 weight %, especially preferred at least 80 weight %, and especially at least 90 weight % are present in the catalyzer of the materials flow that is used for membrane sepn.
The ratio of the polymeric by-products that the reaction zone discharging preferably comprises is no more than 6 weight %, especially preferably is no more than 5 weight %, especially is no more than 4 weight %, based on the gross weight of reaction discharging.
The discharging of reaction zone liquid preferably is not directly used in the membrane sepn in the step b) but at first removes the part component that wherein comprises.Preferably in step b), from the reaction zone discharging, isolate the materials flow of main inclusion compound (I), catalyzer and polymeric by-products.This materials flow is carried out classification by semi-permeable membranes then at least in part.In specific embodiments, this materials flow is divided into the first sub-materials flow and the second sub-materials flow, the first sub-materials flow is recycled in the reaction zone and with the second sub-materials flow carries out classification by semi-permeable membranes.
Before membrane sepn, will be dissolved in carbonic acid gas in the reaction zone discharging and/or the epoxide of general formula I I and from the reaction zone discharging, isolate at least in part.
In addition, preferably will mainly contain reaction product before membrane sepn, i.e. the materials flow of compound (I) is isolated from the reaction zone discharging.
As mentioned above, removing carbonic acid gas and/or epoxide can carry out via the independent gaseous state discharging from reaction zone.If method of the present invention makes up as pure liquid discharging method, then the reaction zone discharging can at first be carried out depressurization steps to isolate carbonic acid gas and/or the epoxide (II) that is dissolved in wherein.Common like this be divided into subsequently the catalyzer of main inclusion compound (I), polymeric by-products, uniform dissolution and if possible the carbonic acid gas of minimal amounts of dissolved and/or epoxide (II) liquid phase and mainly comprise the gas phase of carbonic acid gas and/or epoxide (II).The gas phase that is produced by depressurization steps can partly or entirely be recycled in the reaction zone.This recirculation can or be carried out separately with one gaseous stream that infeeds reaction zone.The liquid phase that obtains in depressurization steps is preferably carried out other classification by ordinary method well known by persons skilled in the art.Preferably liquid phase is distilled materials flow and the mainly materials flow of inclusion compound (I), catalyzer and polymeric by-products to produce main inclusion compound (I).Back one materials flow can be used for membrane sepn then.
This materials flow preferably comprises the boil ratio of by product of height and is no more than 30 weight %, preferably is no more than 25 weight %, especially preferably is no more than 20 weight %, based on the materials flow gross weight of main inclusion compound (I), catalyzer and polymeric by-products.
In specific embodiments, a materials flow is divided into the first sub-materials flow and the second sub-materials flow after inciting somebody to action, and the first sub-materials flow is recycled in the reaction zone and with the second sub-materials flow be used for membrane sepn.
As selection, reaction zone discharging straight-forward fractional distillation can be become:
-mainly comprise the materials flow of unreacted carbonic acid gas and/or epoxide (II),
The materials flow of-main inclusion compound (I) and
The materials flow of-main inclusion compound (I), catalyzer and polymeric by-products.
The fractionation of reaction discharging can be undertaken by ordinary method well known by persons skilled in the art.Be applicable to that fractionated device comprises distillation tower such as tray column, it can provide bubble-cap, sieve plate, screen tray, filler, internals, valve, side-draw device etc.Particularly suitable is the dividing wall column that can provide side-draw device, recirculation etc.Can or be used for distillation with two more than the combination of two distillation towers.Other device that is fit to is vaporizer such as thin-film evaporator, falling-film evaporator, Sambay vaporizer etc. and combination thereof.
Distillation preferred 50-150 ℃ especially, is especially carried out under 70-140 ℃ the bottom temp preferably at about 30-160 ℃.
Distillation can be carried out under normal atmosphere, superatmospheric pressure or decompression.Pressure in the distillation is preferably the 0.0005-1.5 crust, preferred especially 0.001-1.2 crust, especially 0.0-1.1 crust.
In order to isolate polymeric by-products, can obtain the materials flow of also extra inclusion compound (I) and catalyzer in the penetrant (filtrate) that contacts and will comprise polymeric by-products low molecular weight fraction and catalyst-solvent under the pressure with film dorsal part taking-up at film under the pressure lower by the reaction zone discharging than feeding side.Denseer and the solution catalyzer dilution of polymeric by-products high molecular weight block (height boil impurity) obtains as retention.
In preferred embodiments, in the step b) by the classification of film with two or carry out more than two workshop sections (for example with 3,4,5 or 6 workshop sections).
In preferred embodiments, isolated penetrant amount is replenished by liquid is added in the retention at least in part in the film classification.This replenishing can be carried out continuously or discontinuously.Wherein reserved materials does not concentrate but isolated penetrant amount is also referred to as diafiltration by the membrane sepn (ultrafiltration) that replenishes.When in the step b) by the classification of film two or more than two workshop sections in when carrying out, then workshop section, a part of workshop section or all workshop sections can be designed as diafiltration.If product (I) is used for reaction as solvent, then preferably with the liquid of compound (I) as extra introducing in diafiltration.
In another preferred embodiment, do not replenished with the isolated amount of liquid of penetrant in the step b) membrane sepn.Wherein isolated for the purpose of the present invention penetrant amount is not called concentrated by the ultrafiltration that replenishes.When in the step b) by the classification of film two or more than two workshop sections in when carrying out, then workshop section, a part of workshop section or all workshop sections can be designed as concentrated.
In preferred embodiments, the film classification comprises a plurality of workshop sections that connect successively.At this, incoming flow is infeeded in the first film classification (first workshop section), and the materials flow of gained retention is recycled to next workshop section.Finally carry out aftertreatment from the retention materials flow of last workshop section taking-up and obtain comprising the purge flow of polymeric by-products high molecular weight component and the materials flow of being rich in compound (I) and/or solvent.
In specific embodiments, the classification by film in the step b) comprises at first at least one enrichment step and at least one diafiltration steps subsequently.
In addition, the classification by film is preferably carried out continuously in the step b).
Suitable semi-permeable membranes has enough perviousness to the catalyzer that evenly is dissolved in the reaction medium.In addition, they have enough save poweies to the polymeric by-products high molecular weight block that is included in the reaction medium, and promptly they can keep higher molecular weight compound for example oligomeric by epoxide (II) or that polymerization forms.
With at least a separation extreme is 500-20000 dalton, and the preferred daltonian film of 750-10000 dalton, especially 1000-5000 is used for the film classification.The mean pore size of film is generally 0.8-20nm, preferred 0.9-10nm, preferred especially 1-5nm.
The used semi-permeable membranes of the present invention has the separating layer that at least one can comprise one or more materials.These materials are preferably selected from organic polymer, stupalith, metal, carbon and combination thereof.Suitable material is stable under filtration temperature in the charging medium.Preferred film comprises at least a inorganic materials.
Suitable stupalith for example is Alpha-alumina, zirconium white, titanium dioxide, silicon carbide and hybrid ceramic material.
Suitable organic polymer for example is polypropylene, tetrafluoroethylene, polyvinylidene difluoride (PVDF), polysulfones, polyethersulfone, polyetherketone, polymeric amide, polyimide, polyacrylonitrile, regenerated cellulose, polysiloxane polymer.
Particularly preferably in using the mineral membrane of making by a plurality of layers in the inventive method.
Because mechanical reason, usually separating layer is applied on the single or multiple lift porous substrate that comprises with separating layer identical materials or multiple differing materials.The example of possible combination of materials sees the following form:
Special preferable separation layer comprises pottery.
Film in principle can tabular, tubulose, hyperchannel element, kapillary or wound shape solid use, and can utilize to allow isolating convenient pressure shell between retention and the penetrant for this reason.
Best transmembrane pressure between retention and the penetrant depends on film hole diameter, influences the fluid dynamics condition and the mechanical stability of film under filtration temperature of tectum structure.It typically is the 0.2-30 crust, preferred especially 0.5-20 crust.Higher transmembrane pressure causes higher permeation flux usually.If the series connection of a plurality of modules, then the transmembrane pressure of each module can reduce and mates with film thus by increasing permeate pressure.Service temperature depends on the stability of film and the thermostability of charging.Being suitable for the membrane sepn temperature in the step b) is 20-90 ℃, preferred 40-80 ℃.The fusing point of product can the limit temperature scope.Higher temperature causes higher permeation flux usually.Accessible permeation flux greatly depends on type, processing condition, the feed composition (being mainly polymer concentration) of used film and film geometry.Flux is generally 0.5-100kg/m
2/ h, preferred 1.50kg/m
2/ h.For example can use following film:
Membrane sepn in the step b) can in addition the reaction other operate continuously situation under, for example carry out discontinuously by hyperchannel by the film module.Preferred steps b) membrane sepn in for example carries out continuously by the single passage by one or more membrane sepn workshop sections that are connected in series.
The tectal remarkable accumulation of polymeric by-products high molecular weight block that keeps for fear of the film surface causes permeation flux to descend, and it is useful having been found that the mechanical agitation of pumping circulation, film or use agitator between film.These measures are used for the speed of relative movement at film and reaction discharging to be separated generation 0.1-10m/s.
The height impurity that boils can be isolated from retention by known method itself.Preferably retention is distilled to obtain being rich in the purge flow of high boiling compound and the materials flow of being rich in compound (I).Distillation can the known devices of use own as by using at least one short circuit vaporizer to carry out.
By the description of drawings of the preferred embodiment of representing the inventive method, the present invention is not limited to this below the present invention.
Fig. 1 explanation is suitable for carrying out the synoptic diagram of the equipment of the inventive method.
Fig. 2 illustrates the synoptic diagram of two sections film cascades of operate continuously.
Fig. 3 illustrates the synoptic diagram of equipment therefor among the embodiment.
Fig. 1 representative is suitable for carrying out the equipment drawing of the inventive method, and invents incoherent details for clearly former thereby omission with explanation.Equipment comprises the reaction zone (1) that comprises at least one reactor.Epoxide (for example ethylene oxide) is introduced in the reaction zone (1) and with CO via pipeline (2)
2Introduce in the reaction zone (1) via pipeline (3).Discharging (4) taken out from reactor and bring into and handle workshop section (5) via the pipeline that leaves reaction zone (1).In specific embodiments, at first discharging (4) is introduced in the pressure reduction vessel (not shown) wherein be separated into the gas phase that comprises carbonic acid gas and liquid phase.Liquid phase is carried out further aftertreatment in treatment and finishing section (5) subsequently.The gas phase that obtains in the decompression can additionally comprise the unreacted epoxide of part.In treatment and finishing section (5), carry out fractionation to obtain comprising the gas phase (6) of the low component (being mainly carbonic acid gas and/or epoxide) of boiling of reaction discharging, mainly comprise 1, the materials flow (7) of 3-dioxolane-2-ketone (for example ethylene carbonate) and mainly comprise 1, the substrate (8) of 3-dioxolane-2-ketone, catalyzer and reactive polymeric by product.The materials flow (8) that will comprise catalyzer and polymeric by-products is divided into first sub-materials flow (8a) that is recycled to reaction zone (1) and the second sub-materials flow (8b) that infeeds membrane sepn (9).Membrane sepn (9) can have one or more workshop sections.Membrane sepn (9) produces retention materials flow (10), its height that comprises the reactor discharging that keeps by semi-permeable membranes boil component and epoxide and the not isolated catalyzer of small portion if possible.Retention materials flow (10) is infeeded in the treatment and finishing section (11) that designs in specific embodiments as the short circuit vaporizer.The high boiling material materials flow (12) that will obtain in treatment and finishing section (11) is removed from technology.Be rich in 1 with what obtain equally, the materials flow (13) of 3-dioxolane-2-ketone is recycled in the membrane sepn (9).In the first embodiment, what will obtain in membrane sepn (9) mainly comprises 1, and 3-dioxolane-2-ketone, catalyzer and part do not have the penetrant (14) of the high boiling material of reservation to be recycled to treatment and finishing section (5) in membrane sepn (9).In the second embodiment (not shown), penetrant materials flow (14) is recycled in the reaction zone (1).Necessary, live catalyst can be infeeded in the reaction zone (1) via incoming flow (15).
Fig. 2 schematically illustrates the preferred embodiment that comprises the materials flow of catalyzer and high boiling material by two sections film cascade classifications of operate continuously, and wherein two workshop sections can be used as enrichment step (solvent materials flow=0) or diafiltration steps (solvent materials flow=penetrant materials flow) or as concentrating and the mixed form (0＜solvent materials flow＜penetrant materials flow) of diafiltration steps makes up.
To definition based on the operate continuously film workshop section of a workshop section:
Sol=solvent
Perm=penetrant
Diafiltration :=solvent materials flow=penetrant materials flow
Concentrate :=solvent materials flow=0
Comprise diafiltration and spissated mixed form=0＜solvent materials flow＜penetrant materials flow
Concentrate different for described continuous operation mode with same possible batchwise operation pattern with the definition of diafiltration:
Operate continuously:
Diafiltration: solvent materials flow=penetrant materials flow
Mixed form: 0＜solvent materials flow＜penetrant materials flow
Concentrate: solvent materials flow=0
Batchwise operation
Diafiltration: solvent materials flow=penetrant materials flow
Concentrate: solvent materials flow=0
Fig. 3 schematically illustrates the equipment that is used for embodiment and batchwise operation.
The B1=circulation vessel
B2=filtration media reservoir
B3=permeate collection vessels (permeate flow is measured when being used for balance)
The P1=impeller pump
The P2=volume pump
The W1=heat exchanger
The P=pressure survey
The T=temperature survey
The F=flow measurement
The present invention will illustrate by following non-limiting examples.
About using the ceramic multilayer film from Inopor GmbH to carry out the isolated experiment from catalyzer and polymeric by-products low molecular weight fraction of polymeric by-products high molecular weight block, it has mean pore size is that the 3nm and the molecular separation limit are the zirconium dioxide separating layer of 2kD.Use long 50cm and area to be 0.098m
219/3.5 hyperchannel element (having internal diameter in the element is 3.5nm, and 19 holes of film are used in its inside).Use from the ethylene carbonate synthetic contain the hydrogen-catalyst reactor discharging (catalyzer: the bromide salt mixture), wherein by the distillation removed low-boiling-point substance and by the distillation ethylene carbonate is partly isolated.
Contain charging aftertreatment in batches in all experiments of carbonic acid ethyl, catalyzer and polymkeric substance.For this reason, material therefor reached the pressure of 15 crust by pump from circulation vessel and under 70 ℃ temperature with the logical filmed passing tube of the speed of 2m/s, and then be decompressed to normal atmosphere and supply back in the circulation vessel.Under atmospheric pressure isolated penetrant is collected in when balance in the container with the mensuration seepage discharge and by equivalent filtration media (in all experiments is ethylene carbonate) continuous supplementation.Diafiltration usually under about 3 exchange of solvent coefficient MA (promptly under inlet amount x kg) carry out, take out 3x kg penetrant and the 3xkg ethylene carbonate added to make the retention amount keep in the retention constant.Last in experiment, analyze charging and retention.The common negatively charged ion of catalyzer salt mixture (bromide) is used for catalyst analysis.
M
W: weight-average molecular weight (GPC)
HB: high boiling material
Br
-: bromide (potentiometric titration)
The low molecular weight fraction of description of test catalyzer and polymeric by-products can be removed from the charging that comprises catalyzer and polymkeric substance and the high molecular weight block of polymeric by-products can keep by film.Therefore can provide catalyst content low and comprise the higher molecular weight fraction that the materials flow of polymkeric substance and ethylene carbonate is used to remove polymeric by-products.
Claims (22)
1. one kind prepares 1 of general formula I continuously, the method for 3-dioxolane-2-ketone,
Wherein
R
1For hydrogen or have the organic group of 1-40 carbon atom,
R
2And R
3Be hydrogen or C separately independently of each other
1-C
4Alkyl, wherein R
2And R
3Also can mutually combine forms five yuan or six-ring, wherein:
A) epoxide of general formula I I and carbonic acid gas are reacted in liquid phase in the presence of the catalyzer that evenly is dissolved in the liquid phase,
R wherein
1, R
2And R
3As defined above,
B) from reaction zone, take out and comprise the liquid discharging of reactive polymeric by product and comprise by the aftertreatment of semi-permeable membranes fractionated to obtain penetrant and retention, wherein the high molecular weight block tunicle of polymeric by-products keep and
C) provide the purge flow that comprises the polymeric by-products high molecular weight block by retention.
2. according to the process of claim 1 wherein that the low molecular weight fraction of by product enters in the penetrant in step b).
3. according to the method for claim 1 or 2, the materials flow that wherein will comprise catalyzer in step b) except that polymeric by-products is used for the classification by semi-permeable membranes, and wherein catalyzer enters in the penetrant at least in part.
4. according to the method for claim 3, wherein also comprise:
D) penetrant is recycled at least in part in the aftertreatment of the reaction zone of step a) and/or step b).
5. according to each method in the aforementioned claim, wherein in step b), from the reaction zone discharging, isolate the materials flow of main inclusion compound (I), catalyzer and polymeric by-products and carry out classification by semi-permeable membranes at least in part.
6. according to the method for claim 5, wherein will from the reaction zone discharging, the materials flow of isolated main inclusion compound (I), catalyzer and polymeric by-products be recycled in the reaction zone at least in part.
7. according to the method for claim 5 or 6, wherein the materials flow of gaseous stream by isolating the epoxide that mainly comprises unreacted carbonic acid gas and/or general formula (II) from the reaction zone discharging and main inclusion compound (I) obtains the materials flow of main inclusion compound (I), catalyzer and polymeric by-products.
8. according to the method for claim 7, wherein make the reaction zone discharging at first carry out depressurization steps, wherein be divided into the catalyzer of main inclusion compound (I), polymeric by-products, uniform dissolution and the liquid phase and the gas phase that mainly comprises carbonic acid gas and/or epoxide (II) of the carbonic acid gas of minimal amounts of dissolved and/or epoxide (II) if possible, and the distillation liquid phase is with the materials flow that obtains main inclusion compound (I) and the materials flow of main inclusion compound (I), catalyzer and polymeric by-products.
9. according to the method for claim 7, wherein the reaction zone discharging is fractionated into:
-mainly comprise the materials flow of unreacted carbonic acid gas and/or epoxide (II),
The materials flow of-main inclusion compound (I) and
The materials flow of-main inclusion compound (I), catalyzer and polymeric by-products.
10. according to each method in the aforementioned claim, wherein the classification by film is carried out with two or more workshop sections in the step b).
11. according to the method for claim 10, wherein the classification in the step b) comprises at least one diafiltration steps, wherein the liquid of additionally being introduced at least in part in retentate side with the isolated amount of liquid of penetrant replenishes.
12. according to the method for claim 11, wherein with the liquid of compound (I) as extra introducing.
13. according to the method for claim 10, wherein the classification in the step b) comprises at least one enrichment step, wherein the liquid of additionally not introduced with the isolated liquid of penetrant replenishes.
14. according to the method for claim 10, wherein the classification in the step b) comprises the mixed form of diafiltration steps and enrichment step, wherein the liquid of additionally being introduced with the isolated amount of liquid part of penetrant replenishes.
15. according to each method among the claim 10-14, wherein film fractionated workshop section is connected in series.
16. according to each method among the claim 10-15, wherein the classification by film comprises at first at least one enrichment step and at least one diafiltration steps subsequently.
17. according to each method in the aforementioned claim, wherein the classification by film is carried out continuously in the step b).
18. according to each method in the aforementioned claim, be 500-20000 dalton wherein with at least a separation extreme, preferred 750-10000 dalton, the preferred especially daltonian film of 1000-5000 is used for the film classification.
19. according to each method in the aforementioned claim, be 0.8-20nm wherein with at least a aperture, preferred 0.9-10nm, the film of preferred especially 1-5nm is used for the film classification.
20., wherein polymeric film or mineral membrane are used for the film classification according to each method in the aforementioned claim.
21., wherein at least a mineral membranes of being made by a plurality of layers are used for the film classification according to each method in the aforementioned claim.
22. according to each method in the aforementioned claim, it is used to prepare ethylene carbonate or Texacar PC.
Applications Claiming Priority (3)
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| EP08152146 | 2008-02-29 | ||
| EP08152146.0 | 2008-02-29 | ||
| PCT/EP2009/052354 WO2009106605A1 (en) | 2008-02-29 | 2009-02-27 | Membrane separation method for separating high boiler during the production of 1,3-dioxolane-2-ones |
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| Publication Number | Publication Date |
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| CN101965340A true CN101965340A (en) | 2011-02-02 |
| CN101965340B CN101965340B (en) | 2014-09-17 |
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| CN200980107083.1A Expired - Fee Related CN101965340B (en) | 2008-02-29 | 2009-02-27 | Membrane separation method for separating high boiler during the production of 1,3-dioxolane-2-ones |
Country Status (12)
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|---|---|
| US (1) | US20110009645A1 (en) |
| EP (1) | EP2262788B1 (en) |
| JP (1) | JP5787523B2 (en) |
| KR (1) | KR20100124769A (en) |
| CN (1) | CN101965340B (en) |
| BR (1) | BRPI0907545A2 (en) |
| CA (1) | CA2715313C (en) |
| EA (1) | EA201001325A1 (en) |
| ES (1) | ES2566544T3 (en) |
| MX (1) | MX2010008738A (en) |
| TW (1) | TW200942321A (en) |
| WO (1) | WO2009106605A1 (en) |
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| KR101773215B1 (en) | 2009-12-17 | 2017-08-31 | 빈터샬 홀딩 게엠베하 | Method for producing homopolysaccharides |
| EP4378934A1 (en) * | 2021-07-26 | 2024-06-05 | Sumitomo Seika Chemicals Co., Ltd. | Recovery method and production method for cyclic carbonate |
| EP4303255A1 (en) * | 2022-07-07 | 2024-01-10 | RAMPF Eco Solutions GmbH & Co. KG | Processing of plastic solvolysis mixtures |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298401A (en) * | 1998-04-30 | 2001-06-06 | Basf公司 | Method for the continuous production of 1,3-dioxolan-2-ones |
| KR20070016666A (en) * | 2005-08-04 | 2007-02-08 | 최영철 | Membrane Aided Catalytic Coupling Process for Manufacturing Ultra-pure Alkylene Carbonates. |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6384240B1 (en) * | 1998-10-07 | 2002-05-07 | Huntsman Petrochemical Corporation | Process for the purification of alkylene carbonate |
| US20040071968A1 (en) * | 2002-02-25 | 2004-04-15 | Agathagelos Kyrlidis | Porous compositions comprising surface modified monoliths |
| DE10328715A1 (en) * | 2003-06-25 | 2005-01-13 | Basf Ag | A process for the continuous preparation of a compound bearing at least two functional groups |
| DE10328713A1 (en) * | 2003-06-25 | 2005-01-20 | Basf Ag | Process for the separation of a homogeneous catalyst |
| US7784621B2 (en) * | 2004-06-29 | 2010-08-31 | Membrane Technology & Research, Inc | Ultrafiltration membrane and process |
| JP4738786B2 (en) * | 2004-10-01 | 2011-08-03 | 旭化成ケミカルズ株式会社 | Method for producing ethylene carbonate |
| JP4673028B2 (en) * | 2004-10-04 | 2011-04-20 | 旭化成ケミカルズ株式会社 | Method for purifying ethylene carbonate |
| JP4624056B2 (en) * | 2004-10-04 | 2011-02-02 | 旭化成ケミカルズ株式会社 | Continuous production method of alkylene carbonate |
| JP2009537687A (en) * | 2006-05-23 | 2009-10-29 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for producing polyether polyol |
| US8196755B2 (en) * | 2006-06-13 | 2012-06-12 | Basf Se | Process for producing a composite membrane |
| US20100003203A1 (en) * | 2006-10-11 | 2010-01-07 | Basf Se | Method of producing surface-modified nanoparticulate metal oxides, metal hydroxides and/or metal oxyhydroxides |
| CN101641077B (en) * | 2007-03-23 | 2013-01-16 | 巴斯夫欧洲公司 | Method for producing surface-modified nanoparticulate metal oxides, metal hydroxides, and/or metal oxide hydroxides |
| US20100130788A1 (en) * | 2007-05-10 | 2010-05-27 | Basf Se | Method for producing amines |
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2009
- 2009-02-27 CA CA2715313A patent/CA2715313C/en not_active Expired - Fee Related
- 2009-02-27 EA EA201001325A patent/EA201001325A1/en unknown
- 2009-02-27 KR KR1020107020652A patent/KR20100124769A/en active IP Right Grant
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- 2009-02-27 JP JP2010548118A patent/JP5787523B2/en not_active Expired - Fee Related
- 2009-02-27 WO PCT/EP2009/052354 patent/WO2009106605A1/en active Application Filing
- 2009-02-27 ES ES09714427.3T patent/ES2566544T3/en active Active
- 2009-02-27 US US12/867,503 patent/US20110009645A1/en not_active Abandoned
- 2009-02-27 MX MX2010008738A patent/MX2010008738A/en not_active Application Discontinuation
- 2009-02-27 CN CN200980107083.1A patent/CN101965340B/en not_active Expired - Fee Related
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298401A (en) * | 1998-04-30 | 2001-06-06 | Basf公司 | Method for the continuous production of 1,3-dioxolan-2-ones |
| KR20070016666A (en) * | 2005-08-04 | 2007-02-08 | 최영철 | Membrane Aided Catalytic Coupling Process for Manufacturing Ultra-pure Alkylene Carbonates. |
Also Published As
| Publication number | Publication date |
|---|---|
| EA201001325A1 (en) | 2011-02-28 |
| MX2010008738A (en) | 2010-08-31 |
| CA2715313A1 (en) | 2009-09-03 |
| TW200942321A (en) | 2009-10-16 |
| JP5787523B2 (en) | 2015-09-30 |
| BRPI0907545A2 (en) | 2015-07-28 |
| CN101965340B (en) | 2014-09-17 |
| JP2011513281A (en) | 2011-04-28 |
| EP2262788B1 (en) | 2016-02-24 |
| WO2009106605A1 (en) | 2009-09-03 |
| EP2262788A1 (en) | 2010-12-22 |
| KR20100124769A (en) | 2010-11-29 |
| ES2566544T3 (en) | 2016-04-13 |
| US20110009645A1 (en) | 2011-01-13 |
| CA2715313C (en) | 2016-08-02 |
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